Black azo dye.



- UNITED STATES PATENT 'osnron OSCAR DRESSE'L, OF ELBEBFELD, AND RICHARDKOTHE, OF VOHWINKEL, GERMANY ASSIGNORS TO'FARBENFABRIKEN VORM. FRIEDR.BAYER & 00., OF ELBERFELD, GERMANY, A CORPORATION OF GERMANY.

BLACK Azo DYE.

To all whom it may concern: I

sFBe it known that we, OSCAR DRESSEL and RICHARD Koran, doctors ofphilosophy, chemists, citizens of the German Empire, residing at,respectively, Elberfeld and Vohwinkel near Elberfeld, in the Kingdom ofPrussia, Germany, have invented new and useful Improvements in Black AzoDyesyof which the following is a specification.

Our invention relatestolthe manufacture and production of .new black azodyestufis containing once or Specification of Letters Patent.Application filed I'ebruary 4,1907. -Serial No. 356,638.

Patented July 2, 1907.

several times the glycin radical N H- CH CO OH. The process for theirproduction consists in combining the tetrazo-compound of the dyestuff:para aminobenzene-azo-2-amino-S-naphthol-G-sulionic acid either with twomolecules of an azodyestuff component containing the glycin radical(--NH--CH -COOH) or with one molecule of such a compound and onemolecule of any other azodyestuff component, or vice versa or inconverting into the monodiazo compound the disazodyestuffzo-2-amino-Smaphthol-G-sulfonic acid gamma para-pheny1ene( Nn-o r-oooHor with two molecules of. meta-aminotolylglycin NH; v

or with one molecule of one of these compounds and one molecule ofmeta-phenylenediamin or meta-toluylenediamin, or vice versa.

Analogous coloring matters are obtained if in the preceding examplephenylenediamin or 'meta-toluylenediamin are replaced by anotherazo-dyestuff compoj neht, such as, 2-amino-8-naphthol-S-sulfonic acidgamma, 2-amino-5-naphthol-7-sulfonic acid, 1-6- or 1-7- naphthylaminsulfonic acid, substitution products of thesefcompounds, naphtholsulfonic acids, resorcinol,

aminophenols, etc. etc. p

Dyestuffsbf analogous dyeing properties can-also be obtained on carryingout the combination of the above components in any other order ofsuccession e. g'. on combining the diazocompound of para-aminobenzene-1-6-naphthylamin sulfonic acid with one molecule of2-amino-8-naphthol-6-sulfonic acid, diazotizing the coloring matter withone molecule of nitrite and combining thediazo-compound withmeta-aminophenyl- I glycin or meta-aminotolylglycin etc. etc. Instead ofmeta-amino-phenylglyci-n or meta-aminotolylglycin othersuitablecompounds containing the glycin radical can be employed, suchas, glycine of amino-'naphthol sulfonic acids, naphthylamin sulfonicacids, or the like.

The new dyestuffs are dark powders easily soluble in water and dye fullblack shades. Their great aflinity for the vegetable fiber permits animportant simplification in the dyeing of half-woolen goods as itispossible to dye the cotton fiber of such fabrics during the millingprocess full shades, the wool being scarcely tinged at all. Uponreduction with stannous chlorid and hydro chloric acid the new dyestuffsare decomposed paraphenylenediamin and 2-7-diamino-8-naphthol-6-sulfonicacid being two of the products which are formed. In order to carry outthe new process we can proceed as follows, the parts being by weight.. II

Example I.-15 parts of acetyl-para-phenylenediamin are diazotized in theusual manner and the resulting dia zo-compound is introduced into asolution of 24 parts of 2-amino-8-naphthol-6-sulfonic acid gammacontaining an excess of sodium carbonate From the resulting azo-dyestuffthe acetyl group is eliminated in added to a solution of 18 partsofmeta-aminotolylglycin I the usual way by boiling with caustic sodalye. The monoazodyestufi thus produced having the formula:

is then tetrazotized by means of 14 parts of sodium nitrite and thenecessary quantity of H01 and the tetrazocompound thus prepared is mixedwith an aqueous solution of 16,6 parts of meta-aminophenylglyein. Sodiumacetate is added to neutralize the free mineral acid. The intermediatecompound which forms at once is mixed with 24 .parts of 2-amino-8-riaphthol-6- sulfonic acid gamma dissoly'ed in water containing anexcess of sodium carbonate. The mixture is stirred for several hours,the dyestufi is (if necessary salted out), filtered off and dried. Itdyes cotton deep black.

Example II.The tetrazo-compound 0i para-aminobenzene azo- 2 amino 8naphthol- 6- sulfonic acid gamma, the preparation of which is describedin Example I, is mixed with a solution of 30,3 parts of the sodium saltof alphanaphthylglycin-fi-sulfonic acid containing an excess ofsodiu'macetate. When the formation of the intermediate compound iscomplete a solution of 10,8 parts of meta-phenylenediamin is added. Themixture is stirred for some time and then rendered alkaline with sodiumcarbonate. The dyestufi is salted out, filtered off and dried. It dyescotton iull'bluishblack shades.

Example III.-The dyestuff obtained from 15 parts ofacetyl-para-phenylenediamin and 22,3 parts of 1'- naphthylamimG-sulfonicacid is after elimination of the acetyl group nionodiazotized with theaid of 7 parts of sodium nitrite and the necessary quantity ofhydroehlorie acid and the resulting diazo compound is added to anaqueous solution of 24 parts of 2-amino-8-naphtholfi-sulfonic acid gammacontaining an excess of sodium carbonate. When the formation of thedyestuff is complete, it is salted out, filtered, mixed up with waterand rediazotized with the aid of 7 parts of sodium nitrite, and hdrochloric acid. The diazo-compound is thenl containing an excess ofsodium acetate. The-mixture salt is iiltered ofi and dried. It dyescotton bluishblack shades. N

In the following table the shades of some of the new dyestuffs aregiven:

is stirred, rendered alkaline with sodium carbonate and the dyestuifafter complete precipitation with common 5 Dyestuff obtained from: 1moi. para-phenylenediamin+i moi. 2-amino-8-naphthoi-6-sniionic acidgamma (tetrazotized)+ Dyes cotton:

1) 2 moi. meta-aminophenyigiycin Black.

2) 1moi.meta-phenyienediamin-i-imoi. metar- Greenish-biack.

aminophenyigiycin.

1 moi. meta-aminotoiyigiycin-i-i moi. meta- Biuish-biack.

toiuyienediaanin.

1 moi. meta-amino henyigiycin+1 moi. Black.

metai-toiuyienediamin.

1 moi. meta-aminophenylgiycln+1 moi. Black.

meta-aminophenoi. I

1 moi. meta-aminophenyigiycin+ 1 moi. re- Black.

i 'moi. meta-amlnophenyigiycm+i mol. 1- Groenish-biaok.

naphthyiamin-G-sulfonic acid.

irnoi. meta-amino henyigiycin+1 moi. 1- Greenlsh-biack.

ethyiaminonapht aiene-(i-suiionic acid.

1 mol. giycln of the l-riaphthyiamin-dsui- Biulsh-black.

' ionic acid-+1 moi. meta-toiuyienediamin.

10) 1 moi. meta-aminophenyigiycm-l-i moi. 1- Greenish-binck.

naphthyiaminfl-suifonlc acid.

1 mo meta-ammgphenyigiycln+1 moi. 1- Biuish-biack.

hep thoi--snlfo 0 ac d.

1 mo meta-aminophenyiigiycinq-l moi. 2- Blulsh-biack.

naphthobfi suiionic ac 1 mo meta-amino henyigiycin+1 moi. Gr nish-biack.

amino-5-naphtho -7-su1ionic acid.

14) -i moi. meta-amino henyiglycin+i moL Biuish-biack.

amino-S-naphtho -7-su1ionic acid.

1 moi. meta-aminoghenylgiycin+l mp1. Blulsh-biack.

ethyiamlno-6-nap t o -7-sniionic acid.

1 moi. meta-toiuyiene iamin+1 moi. giycin Biulsh-biack.

of the 2-aminos5-na hthoi-7-suiionic acid.

1 moi. meta-aminoto l 1ycln+1'moi. 2-dl- Bluish-biack.

ethyiaminoonapht o -7-suiiomc acid.

1 moi. meta-sminophenyipiycin-ll moi. 2- Biuish-biack.

phenyiarnino-fi-naphtho -7-suiionic acid. 1 moi meta-aminotoiyigiycin+1moi. 2- Biuish-biack.

parptolyiamino -5 naphthoi -7 suiionic Biuish-black.

Biulsh-blilck.

, Having now particularly described our invention and in what manner thesame is to be performed, what we claim as new, and desire to securebyLetters Patent, is:

The herein-described azo dyestuffs, characterized by the giycin radicalNH CHg-COOH, which dyestufis can be obtained by combining thetetrazo'compoundof the dyestuff para amino benzeneazo-2-nmino-'8-naphthoi-(i-suifonic acid with two molecules '0! azodyestuif components, of which at least one must contain the giyclnradical, which dyestulfs are in the shape of their alkaline salts darkpowders, easily soluble in water, dyeing unmordnnied cotton black shadesand beingdecomposed by reduction with stannous chiorid and hydrochloricacid, para-phenylenediamin and 2-7-diainino-8-naphthol-G-sulfonlc acidbeing two of the products which are formed, substantially as described.

In testimony. whereof we have hereunto set our hands in the presence oftwo subscribing witnesses.

- OSCAR DRESSEL. [n s.] RICHARD KOTHE. [n s.]

Witnesses.

O'r'ro Komo, J. A. RITTERSHAUS.

